CN109762200A - Functionality can send out/send out polystyrene bead and preparation method thereof - Google Patents
Functionality can send out/send out polystyrene bead and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of polymer materials, and in particular to and a kind of functionality can send out/send out polystyrene bead and preparation method thereof.Technical problem to be solved by the invention is to provide the preparation methods that polystyrene bead can be sent out/sent out to a kind of functionality, the following steps are included: polystyrene raw material or discarded recycling polystyrene are mixed to obtain pre-composition with function additive, pre-composition is added in supercritical fluid extrusion foaming device, form uniform polymer melt, supercritical fluid is injected in the first extruder end, it is squeezed out by the second extruding dies, then underwater cutpellet is to get polystyrene bead.Conventional foaming method molding can be used in expandable polystyrene bead made from the method for the present invention.The polystyrene foamed material uniform foam cell that the present invention is prepared can be widely applied to the fields such as building, packaging, while also achieve recycling for waste resource.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to and a kind of functionality can send out/send out polystyrene bead
And preparation method thereof.
Background technique
Polystyrene foam plastics (EPS) is wide because of the features such as its is light, easily molded, price is low, sound insulation vibration damping, heat preservation
It is general to be applied to the fields such as construction material, product packaging, food packaging.But since pure polystyrene foam lacks functional, limit
Its application under some particular/special requirement conditions (such as fire-retardant, antistatic, conductive) has been made, therefore has needed to be modified it,
To assign specific function.
Meanwhile most of EPS product category disposable product, it is abandoned after use, can also be generated in process
A large amount of leftover bits, largely discarded EPS is due to its characteristic such as ageing-resistant, anticorrosive, and is difficult to natural degradation, to prevent white
Pollution improves petroleum resources utilization rate, it is necessary to recycle to it.
The recovery method of waste EPS mainly includes following four (plastics science and technology, 2014,42 (2): 122-126.): one,
The broken filling of EPS, the pore former as soil conditioner, compost auxiliary agent, light cement and clay brick；Two, recycling is sorted
EPS clean up after, with fusion method or solvent method make its deaeration recycle, and extruding pelletization prepare EPS reclaimed materials；Three, EPS
Cracking recycling, is made monomers or the oligomer such as styrene, toluene；Four, EPS burns energy regenerating, can partially substitute ironmaking, hair
The fuel of electricity, burning boiler.Currently, EPS discards the price of reclaiming material at 5000 yuan/ton or so, and the price of EPS exists
10000 yuan/ton or so, the EPS cost of material with the functions such as fire-retardant is then higher, therefore can send out poly- by waste EPS preparation function
The economic benefits of styrene beads.Patent CN101701073A discloses a kind of useless with organic solvent dissolution not soluble in water
Old polystyrene realizes that expandable polystyrene particle, antistatic are prepared with magnetic granules of polystyrene, the method
It is disadvantageous in that there are the recycling of organic solvent and Utilizing questions.Patent CN102875734A discloses a kind of recycling grade and can send out
Property the polystyrene and method using seeded polymerization preparation recycling grade expandable polystyrene, this method do not assign and can send out
Property polystyrene functional.Although in conclusion at present about a large amount of patent literature reports of waste EPS recycling, all
There is a problem of more or less.
Currently, the preparation of expandable polystyrene, the method for mostly using suspension polymerisation greatly, are added meeting shadow after solid additive
The stability of the system of sound, this method have certain limitation, be not widely practiced in prepare different function send out polyphenyl second
The particle diameter distribution of alkene, the bead that usual suspension polymerisation obtains is wider, it is necessary to obtain requiring the bead of partial size by screening, but logical
It crosses underwater cutpellet mode and adjusts mouth mold size, the bead of uniform particle sizes can be obtained, this method is simple and fast.By polystyrene raw material
Or discarded recycling polystyrene carries out function modified, and preparation function can send out/polystyrene bead has been sent out, will have boundless
Application prospect.Patent CN104448379A discloses a kind of by the low heat conductive graphite expandability polyphenyl of polystyrene preparation high fire-retardance
The method of ethylene bead material, this method prepare modified polystyrene particle using melt comminution granulation, are then filled using suspending
The modified granules of polystyrene of gas normal direction pours into foaming agent, prepares expandable polystyrene bead, and this method is carried out in two steps,
Complex process, production efficiency are lower.Meanwhile the preparation of polystyrene foam mostly uses alkanes (pentane, butane etc.) foaming agent,
Such foaming agent is inflammable, has certain dangerous.It a kind of is prepared using environmentally friendly, efficient, controllable method it would therefore be highly desirable to develop
Sending out with different functionalities/sent out polystyrene bead.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of polystyrene or recycling polystyrene preparation can
The method for send out/having sent out polystyrene bead.This method is raw material using polystyrene or discarded recycling polystyrene foam, is used
Environmentally protective supercritical fluid (carbon dioxide, nitrogen) is foaming agent, and different function additives is added as needed, using certainly
The supercritical fluid extrusion foaming machine of main research and development squeezes out, and suitable condition is controlled, in conjunction with underwater pellet cutting system, to prepare
Sending out with different functionalities (fire-retardant, antistatic, conductive)/sent out polystyrene bead.The method of the present invention can be sent out squeezing out
Bulb apparatus is connect with underwater pellet cutting system, realizes prosthetic operation substantially, and the product cell density being prepared is uniform, matter
It measures excellent.
First technical problem to be solved by this invention be to provide a kind of functionality can send out/sent out polystyrene bead
Preparation method.The preparation method is the following steps are included: polystyrene or discarded recycling polystyrene are mixed with function additive
Pre-composition, by pre-composition be added to by two concatenated extrusion mechanisms at supercritical fluid extrusion foaming device in, wherein
Be provided with gas injection port on one extruder barrel, First extruder realizes continous way gas injection, guarantee foaming agent steadily inject with
And preventing foaming agent from reversely escaping, second extruder realizes that material uniformly mixes, and sends out by second extruder extrusion/extrusion
Bubble, then underwater cutpellet can send out to get functionality/sent out polystyrene bead.
Preferably, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the polystyrene and function
The additive amount of auxiliary agent are as follows: 50~95wt% polystyrene, 5~50wt% function additive.
Specifically, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the polystyrene is not make
With or recycling polystyrene.The polystyrene of recycling uses after dust removal with machine, impurity removing, washing, drying and other steps processing.
Specifically, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the auxiliary agent is selected from fire-retardant
Agent, antistatic agent, conductive additive, plasticizer, antioxidant.
Further, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, and the fire retardant is poly- phosphorus
Sour ammonium, melamine, melamine phosphate, melamine polyphosphate, melamine cyanurate, expansible graphite, hydrogen
At least one of aluminium oxide, magnesium hydroxide, triphenyl phosphate, montmorillonite, zinc borate or pentaerythrite.
Further, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, and the antistatic agent is second
Glycol lauramide, dodecyl sodium sulfate, monoglycerides, ethoxylated amine, Myrj 45, polyoxyethylene sorbitol
Acid anhydride monostearate, polyether block polyamides copolymer, Sodium Allyl Sulfonate (Atmer 190) or ethoxylated amine (Atmer 163
At least one of or Atmer 262).
Further, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, and the conductive additive is
At least one of carbon black, graphite, carbon fiber, carbon nanotube, graphene oxide or graphene.
Further, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, and the plasticizer is adjacent benzene
At least one of dicarboxylate, dibutyl phthalate, white oil or citrate；The antioxidant is phosphorous acid
Ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010), β-(3,5- di-t-butyls-
4- hydroxy phenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076), N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl)
At least one of propiono) hexamethylene diamine (antioxidant 1098).
It is the fire retardant, antistatic specifically, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead
Agent, conductive modified agent improve using chemical method or physical method the modification of dispersibility.The physical method is heating.It is described
Chemical method be surface preparation, coating modification method, oxidizing process or alkylation process.
Preferably, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, and the extrusion foaming device is adopted
Foaming agent is carbon dioxide or nitrogen.
Preferably, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, when second extruding dies
100~130 DEG C of temperature, 5~40 DEG C of cooling water temperature, underwater pellet cutting system hydraulic pressure is greater than or equal to mouth mold pressure, obtains to send out
Bead；When second 130~170 DEG C of extruding dies temperature, 60~100 DEG C of cooling water temperature, underwater pellet cutting system hydraulic pressure is small
In mouth mold pressure, bead has been sent out.
Specifically, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the polystyrene bead
Partial size is 0.1~3mm.
Specifically, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the continous way gas injection be by
It is realized with flowering structure: including the gas injection port (1) being arranged on First extrusion foaming machine and the gas injection section being arranged on screw rod
(2)；The gas injection port (1) and gas injection section (2) corresponding matching；Screw rod in gas injection section (2) it is arranged circumferentially spaced have it is more
A spiral shell rib (3)；Along the circumferential direction of screw rod, hopper (4) were formed between two neighboring spiral shell rib (3).
Specifically, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the uniform mixing is by following
Structure is realized: the screw rod (21) of second extrusion foaming machine includes dispersion mixing section (36), in dispersion mixing section (36) part
Screw rod (21) on along its axial direction be disposed with non-equidistant segmentation dispersion thread segment (24)；Adjacent two sections of dispersions thread segment
(24) it is located at the screw thread (25) in latter section of dispersion thread segment (24) originates in the last period dispersion thread segment (24) two between
Between screw thread (25).
Preferably, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the First extrusion foaming
The screw speed of machine is 10~100r/min；The screw speed of second extrusion foaming machine is 1~10r/min.
Preferably, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the First extrusion foaming
The temperature of machine is 165~225 DEG C；The temperature of second extrusion foaming machine is 155~170 DEG C.
Preferably, above-mentioned functionality can be sent out/send out in the preparation method of polystyrene bead, the gas injection rate be 2~
15g/100g raw material.
There is provided functionality prepared by the preparation method for second technical problem to be solved by this invention
Can send out/send out polystyrene bead.
It is not related to the use of toxic harmful chemicals solvent, economy during the method for the present invention.The method of the present invention can lead to
It overregulates the conditions such as additive types, mouth mold aperture, temperature, pressure and prepares different sizes, the sending out of different function/send out poly-
Styrene beads.Conventional method (such as steam foaming) molding can be used in gained expandable polystyrene bead.The method of the present invention
It is adaptable, efficiently to provide new method using the recycling of polystyrene and waste polystyrene foam, and impart it
New function has the characteristics that cleaning, easy, economic, environmental-friendly, it is easy to accomplish industrialization production.The method of the present invention is using special
The extrusion foaming machine of different structure screw rod, which prepares functionality, can send out/send out polystyrene bead, extrusion foaming device and underwater cutpellet
System connection is, it can be achieved that basic prosthetic operates, and gained bead abscess is more uniform, and properties of product are better.
Detailed description of the invention
Fig. 1 is the extrusion foaming schematic device that the present invention uses；
Fig. 2 is machine barrel and the structural schematic diagram after screw rod cooperation in First extruder；
Fig. 3 is the cross-sectional view of Section A-A in Fig. 2；
Fig. 4 is the structural schematic diagram of First extruder screw；
Fig. 5 is the enlarged diagram of regional area I in Fig. 4；
Fig. 6 is the cross-sectional view in the section C-C in Fig. 5；
Fig. 7 is the structural schematic diagram of second extruder screw；
Fig. 8 is the enlarged diagram of regional area Q in Fig. 7；
In the figure, it is marked as gas injection port 1, gas injection section 2, spiral shell rib 3, excessively hopper 4, feeding section 5, shielding conveying section 6, the mixing of spiral shell rib
The 7, first extruder 8 of section, gas injection equipment 9, the first machine barrel 10, the first screw rod 12, first charging aperture 13, the first extrusion 14, note
Air pipe 15, the second extruder 18, the second screw rod 21, dispersion thread segment 24, screw thread 25, foaming mouth mold 26, spiral shell rib mixing section 35,
Dispersion mixing section 36.
Specific embodiment
The preparation method of polystyrene bead can be sent out/sent out to functionality of the present invention, comprising the following steps: will be not used poly-
Styrene or through dust removal with machine, impurity removing, washing, drying and break process recycling waste polystyrene foamed plastics with have
The function additive of different function mixes to form pre-composition, and the supercritical fluid extrusion foaming that pre-composition is added to independent research is filled
In setting, 165~180 DEG C of First extruder temperature, 10~100r/min of screw speed are controlled, pre-composition forms uniform molten
Body injects supercritical fluid aerating powder, gas foaming agent gas injection rate 2~15g/100g raw material in First extruder end；Control
155~170 DEG C of second extruder temperature is made, 1~10r/min of screw speed keeps foaming agent uniform with melt mixed, and material is logical
The second extruding dies extrusion/extrusion foaming is crossed, and obtains needing size through underwater pellet cutting system progress pelletizing or water ring pelletizing
The spherical or ellipsoid bead of (such as 0.1~3mm), can be obtained can send out or send out polystyrene bead.By regulation gas injection rate,
Extrusion temperature and pelletizing condition control foaming situation, to obtain can send out or send out polystyrene bead.
In the method for the present invention, if function additive dosage is too low, product cannot reach expected performance；If function additive
Dosage is excessively high, and there are certain wastes, while influencing processing performance, and foam performance is deteriorated.Such as with flame retardant polystyrene foam
For, when amount of flame-retardant agent is less than 10wt%, poor flame retardant properties, oxygen index (OI) is only 20.86%, cannot reach UL-94V-0
Grade；When adding 30wt% fire retardant, preferable flame retardant property can be obtained, oxygen index (OI) is greater than 30%, can achieve UL-94V-0
Grade.If continuing the additive amount of increase fire retardant, foam performance can be had an impact, expansion ratio is decreased obviously.It is preferred that control is poly-
The proportionate relationship of styrene and auxiliary agent is 50~95wt% polystyrene, 5~50wt% auxiliary agent.
The function additive is function additive commonly used in the art, such as fire retardant, antistatic agent, conductive additive, plasticising
Agent, antioxidant.The fire retardant is also fire retardant commonly used in the art, such as ammonium polyphosphate, melamine, melamine phosphoric acid
Salt, melamine polyphosphate, melamine cyanurate, expansible graphite, aluminium hydroxide, magnesium hydroxide, triphenyl phosphate,
Montmorillonite, zinc borate, pentaerythrite.The antistatic agent is also antistatic agent commonly used in the art, as ethylene glycol lauroamide,
Dodecyl sodium sulfate, monoglycerides, ethoxylated amine, Myrj 45, polyoxyethylene sorbitan monostearate,
Polyether block polyamides copolymer, Sodium Allyl Sulfonate (Atmer 190), ethoxylated amine (Atmer 163 or Atmer 262).
The conductive agent is also conductive agent commonly used in the art, such as carbon black, graphite, carbon fiber, carbon nanotube, graphene oxide or graphite
Alkene.The plasticizer also selects plasticizer commonly used in the art, and the antioxidant also selects antioxidant commonly used in the art.
The fire retardant, antistatic agent, conductive modified agent, plasticizer, antioxidant carry out improving dispersibility using chemical method or physical method
Modification.The physical method is heating.The chemical method is surface preparation, coating modification method, oxidizing process or alkyl
Change method.Those skilled in the art can need to be added different function additives according to different.
In the method for the present invention, conventional supercritical fluid foaming agent is can be used in the extrusion foaming device, such as carbon dioxide, nitrogen
Gas.
In the method for the present invention, two kinds of polystyrene beads can have been sent out or can have been sent out, can have been controlled by control gas injection rate
Foaming agents content in system processed, to achieve the purpose that control expansion ratio.Extruding dies temperature is adjusted, also can achieve
The purpose of expansion ratio is controlled, when principle is that die temperature is higher, melt viscosity is smaller, is conducive to foam, and expansion ratio is high；
When die temperature is lower, melt viscosity is big, and foaming is more difficult, and expansion ratio is small or does not foam.Polymer melt is leaving mouth
It after mould, is cut rapidly by underwater pelletizer cutter head, by regulation water pressure and water temperature, can control bead in cooling procedure
Foam situation.In the process, if die temperature is high, hydraulic pressure is smaller, and water temperature is higher, has the sufficient time to send out polymer melt
Bubble, therefore sent out bead；If die temperature is low, hydraulic pressure is larger, and water temperature is lower, after polymer melt is cut, is recycling
Under cooling water effect, beadlet temperature is rapidly decreased to glass transition temperature hereinafter, cannot foam, and obtains that bead can be sent out.Preferably,
When 100~130 DEG C of die temperature, 5~40 DEG C of water temperature, underwater pellet cutting system hydraulic pressure is greater than or equal to mouth mold pressure, obtains to send out
Bead；When 130~170 DEG C of die temperature, 60~100 DEG C of cooling water temperature, underwater pellet cutting system hydraulic pressure is less than mouth mold pressure, obtains
To having sent out bead.
In the method for the present invention, the supercritical fluid extrusion foaming device of used independent research uses two extrusion foamings
The concatenated mode of machine is carried out squeezing out/extrusion foaming, then is connect with underwater pellet cutting system.Wherein, First foaming machine is main
Realize melting pre-composition and realize continous way gas injection purpose, continous way gas injection be in order to guarantee foaming agent steadily inject and prevent
Only foaming agent reversely escapes；First discharge port is connect with second feed inlet, realizes the string of First and second extruder
Connection；Second extruder mainly cools down and full and uniform mixed purpose, simultaneously because extending the stop of material in a device
Time is to reduce temperature.
Further, to achieve the goals above, the screw speed of the First extrusion foaming machine is 10~100r/
min；The screw speed of second extrusion foaming machine is 1~10r/min.The temperature of the First extrusion foaming machine is
165~180 DEG C；The screw speed of second extrusion foaming machine is 155~170 DEG C.
Further, the continous way gas injection is by being realized with flowering structure: including being arranged on First extrusion foaming machine
Gas injection port (1) and the gas injection section (2) that is arranged on screw rod；The gas injection port (1) and gas injection section (2) corresponding matching；In gas injection
The arranged circumferentially spaced of screw rod in section (2) has multiple spiral shell ribs (3)；Along the circumferential direction of screw rod, between two neighboring spiral shell rib (3)
Formed hopper (4).When due to conventional gas injection, it is possible that the case where premix pressure is greater than gas injection pressure, premixes herein
Material is easily accessible air injection pipe, to then need to increase air pressure and go out the material entered in air injection pipe gas injection blockage.This hair
Screw rod is set using the above structure in bright method, when the rotation of First extruder screw, spiral shell rib (3) is connected with gas injection port (1),
To realize closing, continue then pressure rise of ventilating, as screw rod rotates, crosses hopper (4) and be connected with gas injection port (1), to release
The gas of deflation body, elevated pressures is gone out, so that material will not block pipe, finally realizes the stable continous way note of gas injection pump
Gas.
Further, the full and uniform mixing with flowering structure by being realized: screw rod (21) packet of second extrusion foaming machine
Dispersion mixing section (36) have been included, have been disposed with non-equidistant point along its axial direction on the screw rod (21) of dispersion mixing section (36) part
The dispersion thread segment (24) of section；The screw thread being located in latter section of dispersion thread segment (24) between adjacent two sections of dispersions thread segment (24)
(25) originate between two screw threads (25) in the last period dispersion thread segment (24).When second extruder screw rotation, spiral shell
The protrusion of line (25) realizes the purpose that material mixes well.
Preferably, the gas injection rate is 2~15g/100g raw material.
Extrusion foaming device screw rod of the present invention is the screw rod on foam device；Due to foam device
It needs to inject foaming agent, therefore needs to be provided with corresponding 1 structure of gas injection port on foam device, as shown in Fig. 3
The gas injection port 1 being arranged on one machine barrel 10.Gas injection port 1 is for injecting foaming agent into extrusion channel so that foaming agent and extrusion are logical
Material melt in road is sufficiently mixed rear extrusion molding foamed products.Material melt therein is usually thermal plastic high polymer polymerization
Object material；In addition corresponding nucleating agent, plasticizer or other materials component can also be added as needed；And foaming agent is then usual
It can be used as one or more of supercritical carbon dioxide, nitrogen gas and water, butane, pentane, depending on needed for product,
There is no stringent limitations.
Screw rod of the present invention is equipped with feed end and discharge end along the extrusion direction of screw rod on screw rod, is feeding
Gas injection section 2 corresponding with the gas injection port 1 on extrusion foaming device is equipped between end and discharge end；Screw rod in gas injection section 2
It is arranged circumferentially spaced to have multiple spiral shell ribs 3；Along the circumferential direction of screw rod, hopper 4 was formed between two neighboring spiral shell rib 3.Specifically may be used
Referring to shown in attached drawing 4 to attached drawing 6, wherein screw rod of the present invention after mounting its gas injection section 2 should on foam device
Gas injection port 1 it is corresponding, can refer to as shown in attached drawing 2 and attached drawing 3, in this way when screw rod during rotation, gas injection port 1 will between
Every ground respectively with spiral shell rib 3 and cross 4 corresponding matching of hopper, and then gas injection port 1 can realize discontinuously with cross hopper 4 be connected to；And punishment in advance
Slot 4 is then the channel that material melt passes through, therefore when corresponding mistake hopper 4 turns to connection corresponding with gas injection port 1, Ji Keshi
Now foaming agent is injected into the material melt crossed in hopper 4；And when corresponding spiral shell rib 3 turns to Shi Zeke corresponding with 1 pair of gas injection port
The temporary plugging to gas injection port 1 is realized by spiral shell rib 3.In addition, in order to ensure there is preferable plugging effect, spiral shell to gas injection port 1
The finish dimensional of gas injection port 1 should be not less than on rib 3 with the size of 1 matching part of gas injection port；And according to spiral shell rib 3 and gas injection port 1
The size relationship at upper relative engagement position determines that each spiral shell rib 3 is long to the blocking time of gas injection port 1 in combination with the revolving speed of screw rod
Degree.By spiral shell rib 3 to the temporary plugging of gas injection port 1, then can play the role that by compartment of terrain block gas injection port 1, it can be achieved that
It is regularly spaced gas injection, and may make the gas injection pressure of gas injection port 1 that in the fluctuating change of regularity, it is every that gas injection port 1 can be increased
Pressure when secondary gas injection, and then can be relieved material melt and block gas injection port 1, it is ensured that gas injection effect and prevent material melt from note
Port reversely overflows, to finally realize the stable continous way gas injection of gas injection pump.
In addition, without loss of generality, in order to ensure screw rod effectively rotates in the machine barrel of extruder, screw rod after mounting with machine
Should theoretically have certain gap between cylinder, therefore above-mentioned spiral shell rib 3 is turned to and infused during rotating with screw rod
When 1 corresponding matching of port, theoretically may there are certain gaps, but can by setting spiral shell rib 3 and gas injection port 1 between
To approach zero clearance cooperation to ensure spiral shell rib 3 to the plugging effect of gas injection port 1.
It is furthermore preferred that set spiral shell rib 3 can be to be arranged evenly and at intervals, at this time institute along the circumferential direction of screw rod in the present invention
The hopper 4 of crossing of formation is also evenly spaced distribution, in this way when screw rod is during uniform rotation, the pressure at gas injection port 1
The frequency of fluctuation and gas injection will appear as uniform variation, so that gas injection process is more uniform, steady.And theoretically, originally
Invention in the quantity along the circumferentially spaced spiral shell rib 3 of screw rod there is no stringent limitation, theoretically at least one settable spiral shell
Rib 3 will form one accordingly and cross hopper 4；Or may also set up multiple spiral shell ribs 3, multiple hoppers excessively will be will form accordingly
4；Such as it may be configured as 4-8 spiral shell rib 3, or be preferably arranged to 6 spiral shell ribs 3.
In addition, the circumferential direction along screw rod can be further disposed at, range shared by each spiral shell rib 3 crosses model shared by hopper 4 with each
The ratio between enclose is 0.5-2 times.Pass through the gas injection duration and closure of adjusting spiral shell rib 3 and the size realization adjusting gas injection port 1 for crossing hopper 4
Ratio between duration, and then achieve the purpose that adjust gas injection effect.
In addition, can meet for the shape of each spiral shell rib 3, when as long as cooperating when theoretically it is rotated with gas injection port 1 to note
Effective temporary plugging of port 1 simultaneously can keep certain closure duration in the further rotation process with screw rod.It can
In the radial direction observation along screw rod, the spiral shell rib 3 is in rectangle, parallelogram；Certainly, without loss of generality, spiral shell rib 3 can also
In other shapes for meeting above-mentioned requirements.
In addition, it is generally the case that the screw rod for extrusion foaming device squeezes out the usual subsection setup in direction on edge, and general
It is disposed with feeding section 5, shielding conveying section 6 and spiral shell rib mixing section 7；The gas injection section 2 being arranged in the present invention at this time is preferably set
It is placed in spiral shell rib mixing section 7 and leans on the first segment spiral shell rib position of 6 one end of close shield conveying section；Gas injection section 2 i.e. in the present invention is practical
For one section a portion on spiral shell rib mixing section 7 near close shield conveying section 6.The benefit being arranged in this way has: on the one hand may be used
In gas injection process, the foaming agent that injection can be effectively prevented from by shielding conveying section 6 is flowed to 5 direction of feeding section, another party
Face also may make after injecting foaming agent, then be carried out material melt and foaming agent centainly by subsequent spiral shell rib mixing section 7
Immixture.
Spiral shell rib mixing section described in aforementioned present invention 7, material melt after being mainly used for injecting foaming agent with
Foaming agent is mixed, to improve its mixing efficiency.It can be by the part in spiral shell rib mixing section 7 in addition to gas injection section 2 in the present invention
Be set as from the identical structure type of gas injection section 2 or different structure type, as long as ensuring spiral shell rib mixing section 7 to material melt
With effectively mixing for foaming agent.Referring to shown in attached drawing 5, set for the part in spiral shell rib mixing section 7 in addition to gas injection section 2
It is set to structure type identical with gas injection section 2, can be used in gas injection section 2 in all spiral shell ribs of 7 whole interior of spiral shell rib mixing section
Spiral shell rib structure；Certainly, in order to ensure the mixed effect in spiral shell rib mixing section 7, can in the axial direction along screw rod, adjacent spiral shell rib it
Between can there are certain spacing.
In addition, the present invention plants extrusion foaming device, including the first extruder 8 and gas injection equipment 9 referring to shown in attached drawing 1,
Gas injection equipment 9 is for injecting foaming agent into the first extruder 8, wherein foaming agent can be used as supercritical carbon dioxide, nitrogen
One or more of gas and water, butane, pentane.Gas injection equipment 9 generallys use high-pressure gas injection pump and carries out gas injection.Described first
Extruder 8 includes the first machine barrel 10, has first to squeeze out channel in the first machine barrel 10, is provided with the in the first extrusion channel
One screw rod 12 is provided with the first charging aperture 13 being connected to respectively with the first extrusion channel, the first extrusion on the first machine barrel 10
14 and gas injection port 1.Specific workflow are as follows: material is entered in the first extrusion channel by first charging aperture 13, then by
The rotation of first screw rod 12 by material first extrusion channel in push and by be arranged in the bringing-up section outside the first machine barrel 10 into
Row is heated in material melt state；It is squeezed out later by gas injection port 1 from gas injection equipment 9 to first in the material melt in channel
Foaming agent is injected, then by being discharged from the first extrusion 14 after being sufficiently mixed of foaming agent and material melt.
Extrusion foaming device described in aforementioned present invention, the first screw rod 12 therein are to use extrusion of the present invention
Foam device screw rod, while the first charging aperture 13 is corresponding with 12 upper feeding end of the first screw rod, first extrusion 14
Corresponding with the discharge end of the first screw rod 12, the gas injection port 1 is corresponding with the gas injection section 2 on the first screw rod 12；The gas injection equipment 9
It is connected by gas injection pipeline 15 with gas injection port 1；It in this way can be by being set in gas injection section 2 on the first screw rod 12 and the first machine barrel 10
Gas injection is realized after the cooperation for the gas injection port 1 set.
In addition, also further check valve can be provided on gas injection pipeline 15；It in this way can be when preventing gas injection to a certain degree
Counter flow action.
In addition, the quantity for the gas injection port 1 being arranged on the first machine barrel 10 can be provided with one or more according to actual needs
It is a, and when being provided with multiple can by multiple gas injection ports 1 on the first machine barrel 10 along the circumferentially-spaced distribution of the first screw rod 12.
Certainly, multiple gas injection ports 1 should all be corresponding with the gas injection section 2 on the first screw rod 12 respectively.As referring to institute in attached drawing 2 and attached drawing 3
Show, on the first machine barrel 10 setting there are two gas injection port 1, and further by two gas injection ports 1 on the first machine barrel 10 phase
Axisymmetrical distribution for the first screw rod 12.
In addition, extrusion foaming device of the present invention, may also include has the second extruder 18, second extruder 18
It connects with the first extruder 8, the first extrusion 14 on the first extruder 8 is corresponding with the feed inlet on the second extruder 18 to be connected
It is logical；Foaming mouth mold 26 is provided at the extrusion on the second extruder 18.Two extruders are led in this way, the present invention realizes
It crosses series system to be attached, it is ensured that after being sufficiently mixed between effective gas injection of foaming agent and foaming agent and melt material
Using foaming 26 extrusion molding of mouth mold, the operation stability of extrusion foaming device is improved.
More specifically, in order to improve the second screw rod 21 to the immixture effect of material melt and foaming agent, in the present invention
It includes dispersion mixing section 36 that second screw rod 21, which is further arranged, the edge on the second screw rod 21 of 36 part of dispersion mixing section
Its axial direction is disposed with the dispersion thread segment 24 of non-equidistant segmentation；It is located at latter section point between adjacent two sections of dispersions thread segment 24
The screw thread 25 in thread segment 24 is dissipated to originate between two screw threads 25 in the last period dispersion thread segment 24；Specific structure can refer to
Shown in attached drawing 7 and attached drawing 8；And so-called non-equidistant segmentation, that is, refer to the length distance of dispersion thread segment 24 axially along a screw not
Essentially equal, there are certain variations.In this way, can ensure that the second screw rod 21 to foaming agent by the way that 36 structure of dispersion mixing section is arranged
With being sufficiently mixed for material melt.In addition, in the present invention on the second screw rod 21, it can also be along direction be squeezed out, in dispersion mixing section
36 downstream is provided with corresponding spiral shell rib mixing section 35, and the effect of spiral shell rib mixing section 35 is also to further increase to foaming agent and object
Material solution is sufficiently mixed effect, and the structure of the screw thread mixing section 35 may be configured as in same spiral shell rib mixing section 7 except gas injection section 2
With the identical structure type of outer portion.
In addition, the first screw rod 12 in the present invention and the second screw rod 21 can also be according to be associated withs setting as follows: being arranged described the
The screw diameter ratio of one screw rod 12 and the second screw rod 21 is 1:1.25~1:3；Simultaneously in actual moving process, the first spiral shell is set
The range of speeds of bar 12 is 10~150 revs/min, and the range of speeds of the second screw rod 21 of setting is 1~30 rev/min, and full
The rotating ratio range of the first screw rod 12 of foot and the second screw rod 21 is 1:5~1:50.Certainly, above-mentioned first screw rod 12 and the second spiral shell
The respective revolving speed of bar 21 and the rotating ratio of the two can carry out adjustment appropriate according to specific operating condition.Pass through above-mentioned association
Setting may make the first extruder 8 to operate in relatively high screw speed to realize good plasticizing and the foaming agent of material
Quick and stable injection, and material melt is mixed with the preliminary of foaming agent；And the second extruder 18 operate in it is relatively low
Revolving speed so that situations such as material melt and foaming agent have more incorporation times and reduce temperature and pressure fluctuation.More specifically
, when for specific to the first screw rod 12, it is 1:25~1:40 that its draw ratio, which may further be provided,；And for the second screw rod
21, its settable draw ratio is 1:20~1:30.
In addition, the present invention further can also be provided with circulating cooling section on the first machine barrel 10, set in circulating cooling section
It is equipped with cooling liquid flowing channel, and circulating cooling section is corresponding with the feeding section 5 on the first screw rod 12.Circulating cooling section can be arranged
On first machine barrel 10 in closely 13 downstream of first charging aperture.By being passed through corresponding cooling medium into cooling liquid flowing channel 7, such as
Cooling water；It can be achieved to control the temperature of the material in circulating cooling section, therefore for the material containing volatile component,
It can effectively prevent the volatilization of volatile ingredient.Certainly, specifically whether control the temperature of material using circulating cooling section, it can root
Depending on specific material situation.
Heretofore described foaming mouth mold 26 generally can be used according to the difference of required extrusion molding product as hair
The various conventional foaming die geometry forms such as tubule mouth mold, foaming sheet die or foaming annular die.
In addition, it is generally the case that in order to ensure material maintains certain temperature condition in foaming mouth mold 26, can also send out
Bubble mouth mold 26 on be provided with corresponding temperature regulating device and sensor etc., specifically can according to the actual situation depending on.
Embodiment 1
Polystyrene is mixed with fire retardant, used composite material proportion are as follows: 73.53wt% polystyrene,
Pre-composition is added directly into supercritical fluid extrusion foaming dress by 24.51wt% expansible graphite, 1.96wt% triphenyl phosphate
It sets middle melting extrusion to foam, 165~180 DEG C, screw speed 40r/min of first segment extruder temperature range, carbon dioxide gas injection
Measure 5g/100g raw material；155~170 DEG C of second segment extruder temperature range, is led to by 100 DEG C of die temperature, screw speed 8r/min
Underwater cutpellet is crossed, 35 DEG C of circulating cooling coolant-temperature gage, obtains the Modified by Expandable Graphite expandable polystyrene bead that partial size is 1mm.
Every kilogram of recycling grade expandable polystyrene raw material adds surface coating agent zinc stearate 4g.
Bead can be sent out to be placed in Simple foaming device, using vapor foamable, 126 DEG C of forming temperature, when continuing
Between 10min, mold is taken out, and carry out water cooling from foam device, obtains polystyrene foamed material.
Foam density obtained by the present embodiment is 56.78kg/m3, flame retardant rating is up to HF1 grades of horizontal firing, vertical combustion V-
0 grade.
Embodiment 2
The waste polystyrene foamed plastics of recycling through dust removal with machine, impurity removing, washing, drying and are crushed, are used
Composite material proportion are as follows: 44.12wt% polystyrene, 29.41wt% waste polystyrene foam, 15.69wt% are inflatable
Graphite, 8.82wt% melamine phosphate, 1.96wt% triphenyl phosphate, are added directly into supercritical fluid for pre-composition and squeeze
Melting extrusion is foamed in foam device out, and 165~180 DEG C, screw speed 40r/min of first segment extruder temperature range, dioxy
Change carbon gas injection rate 8g/100g raw material；155~170 DEG C of second segment extruder temperature range, 100 DEG C of die temperature, screw speed
8r/min, by underwater cutpellet, 35 DEG C of circulating cooling coolant-temperature gage, polyphenyl can be sent out by obtaining the Modified by Expandable Graphite that partial size is 1mm
Ethylene bead.Every kilogram of recycling grade expandable polystyrene raw material adds surface coating agent zinc stearate 4g.
Bead can be sent out to be placed in Simple foaming device, using vapor foamable, 126 DEG C of forming temperature, when continuing
Between 10min, mold is taken out, and carry out water cooling from foam device, obtains polystyrene foamed material.
Foam density obtained by the present embodiment is 47.36kg/m3, flame retardant rating is up to HF1 grades of horizontal firing, vertical combustion V-
0 grade.
Embodiment 3
The waste polystyrene foamed plastics of recycling through dust removal with machine, impurity removing, washing, drying and are crushed, are used
Composite material proportion are as follows: 73.53wt% waste polystyrene, 16.34wt% expansible graphite, 8.17wt% melamine phosphorus
Pre-composition is added directly into melting extrusion in supercritical fluid extrusion foaming device and sent out by hydrochlorate, 1.96wt% triphenyl phosphate
Bubble, 165~180 DEG C, screw speed 40r/min of first segment extruder temperature range, nitrogen gas injection rate 6g/100g raw material；Second
155~170 DEG C of range of extruder temperature of section, 150 DEG C of die temperature, screw speed 8r/min passes through underwater cutpellet, circulating cooling
It 80 DEG C of coolant-temperature gage, obtains the Modified by Expandable Graphite that partial size is 3mm and has sent out polystyrene bead.
Bead will have been sent out to be placed in Simple foaming device, using vapor hot briquetting, 126 DEG C of forming temperature, when continuing
Between 10min, mold is taken out, and carry out water cooling from foam device, obtains polystyrene foamed material.
Foam density obtained by the present embodiment is 51.36kg/m3, flame retardant rating is up to HF1 grades of horizontal firing, vertical combustion V-
0 grade.
Embodiment 4
The waste polystyrene foamed plastics of recycling through dust removal with machine, impurity removing, washing, drying and are crushed, are used
Composite material proportion are as follows: 85wt% polystyrene, 10wt% antistatic agent Atmer 190,5wt% antistatic agent Atmer
163, pre-composition is added directly into melting extrusion in supercritical fluid extrusion foaming device and is foamed, first segment extruder temperature model
165~180 DEG C, screw speed 40r/min are enclosed, nitrogen gas injection rate 4g/100g raw material；Second segment extruder temperature range 155~
170 DEG C, 150 DEG C of die temperature, screw speed 8r/min, by underwater cutpellet, 80 DEG C of circulating cooling coolant-temperature gage, obtaining partial size is
The antistatic modified of 2mm has sent out polystyrene bead.
Bead will have been sent out to be placed in Simple foaming device, using vapor hot briquetting, 126 DEG C of forming temperature, when continuing
Between 10min, mold is taken out, and carry out water cooling from foam device, obtains polystyrene foamed material, surface resistivity 5
×109Ω。
Embodiment 5
The waste polystyrene foamed plastics of recycling through dust removal with machine, impurity removing, washing, drying and are crushed, are used
Composite material proportion are as follows: 71.43wt% polystyrene, 23.81wt% carbon fiber, 4.76wt% silane coupling agent KH560, will
Pre-composition is added directly into melting extrusion in supercritical fluid extrusion foaming device and foams, first segment extruder temperature range 165
~180 DEG C, screw speed 40r/min, carbon dioxide gas injection rate 5g/100g raw material；Second segment extruder temperature range 155~
170 DEG C, 150 DEG C of die temperature, screw speed 8r/min, by underwater cutpellet, 80 DEG C of circulating cooling coolant-temperature gage, obtaining partial size is
The conductive modified of 2mm has sent out polystyrene bead.
Bead will have been sent out to be placed in Simple foaming device, using vapor hot briquetting, 126 DEG C of forming temperature, when continuing
Between 10min, mold is taken out, and carry out water cooling from foam device, obtains polystyrene foamed material, conductivity 1s/cm.
Claims (10)
1. the preparation method that polystyrene bead can be sent out/sent out to functionality, it is characterised in that: the following steps are included: by polyphenyl second
Alkene or discarded recycling polystyrene mix to obtain pre-composition with function additive, and pre-composition is added to by two concatenated extrusion mechanisms
At supercritical fluid extrusion foaming device in, gas injection port, First extruder are wherein provided on First extruder barrel
It realizes continous way gas injection, guarantees that foaming agent steadily injects and prevents foaming agent from reversely escaping, second extruder realizes material
Uniformly mixing, by second extruder extrusion/extrusion foaming, then polyphenyl second can be sent out/sent out to underwater cutpellet to get functionality
Alkene bead.
2. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 1, it is characterised in that: institute
State the additive amount of polystyrene and function additive are as follows: 50~95wt% polystyrene, 5~50wt% function additive.
3. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 1 or 2, it is characterised in that:
The function additive is selected from fire retardant, antistatic agent, conductive additive, plasticizer, antioxidant.
4. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 3, it is characterised in that: institute
State fire retardant be ammonium polyphosphate, melamine, melamine phosphate, melamine polyphosphate, melamine cyanurate,
At least one of expansible graphite, aluminium hydroxide, magnesium hydroxide, triphenyl phosphate, montmorillonite, zinc borate or pentaerythrite；
The antistatic agent is ethylene glycol lauroamide, dodecyl sodium sulfate, monoglycerides, ethoxylated amine, polyoxyethylene 8 stearate
In ester, polyoxyethylene sorbitan monostearate, polyether block polyamides copolymer, Sodium Allyl Sulfonate or ethoxylated amine
It is at least one；The conductive additive be carbon black, graphite, carbon fiber, carbon nanotube, graphene oxide or graphene at least
It is a kind of；The plasticizer is at least one in diethyl phthalate, dibutyl phthalate, white oil or citrate
Kind；The antioxidant is phosphite ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propionyl
At least one of base) hexamethylene diamine.
5. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 1, it is characterised in that: institute
Stating foaming agent is carbon dioxide or nitrogen, and gas injection rate is 2~15g/100g raw material.
6. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 1, it is characterised in that: when
Second 100~130 DEG C of extruding dies temperature, 5~40 DEG C of cooling water temperature, underwater pellet cutting system hydraulic pressure is greater than or equal to mouth
Molding pressure obtains that bead can be sent out；When second 130~170 DEG C of extruding dies temperature, 60~100 DEG C of cooling water temperature, under water
Pelletizing system hydraulic pressure is less than mouth mold pressure, has been sent out bead.
7. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 1, it is characterised in that: institute
The temperature for stating First extrusion foaming machine is 165~225 DEG C；The temperature of second extrusion foaming machine is 155~170 DEG C；
The screw speed of the First extrusion foaming machine is 10~100r/min；The screw speed of second extrusion foaming machine is
1~10r/min.
8. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 1, it is characterised in that: institute
Stating continous way gas injection is by being realized with flowering structure: being existed including the gas injection port (1) being arranged on First extrusion foaming machine and setting
Gas injection section (2) on screw rod；The gas injection port (1) and gas injection section (2) corresponding matching；The circumferential direction of screw rod in gas injection section (2)
It has been positioned apart from multiple spiral shell ribs (3)；Along the circumferential direction of screw rod, hopper (4) were formed between two neighboring spiral shell rib (3).
9. the preparation method that polystyrene bead can be sent out/sent out to functionality according to claim 1, it is characterised in that: institute
Uniformly mixing is stated by realizing with flowering structure: the screw rod (21) of second extrusion foaming machine includes dispersion mixing section (36), is being divided
Dissipate the dispersion thread segment (24) for being disposed with non-equidistant segmentation on the screw rod (21) of mixing section (36) part along its axial direction；It is adjacent
It is located at the screw thread (25) in latter section of dispersion thread segment (24) between two sections of dispersions thread segment (24) and originates in the last period dispersion spiral shell
Between two screw threads (25) in line section (24).
10. the functionality being prepared by preparation method according to any one of claims 1 to 9 can send out/send out polystyrene bead
Grain.
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| CN109762200B (en) | 2021-08-06 |
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